WO2005095554A1

WO2005095554A1 - Hydrocarbon oil for hydrogen production and hydrogen production system

Info

Publication number: WO2005095554A1
Application number: PCT/JP2005/006706
Authority: WO
Inventors: Tadahide Sone; Masanori Hirose; Osamu Sadakane; Iwao Anzai
Original assignee: Nippon Oil Corporation
Priority date: 2004-03-31
Filing date: 2005-03-30
Publication date: 2005-10-13
Also published as: KR101163249B1; KR20060133063A

Abstract

A hydrocarbon oil comprising a hydrocarbon base which is produced at least through the step of subjecting a hydrocarbon mixture having specific properties to hydrodesulfurization under specific conditions, the step of removing light matters from the oil which has undergone the hydrodesulfurization, and the step of removing at least a given amount of linear saturated hydrocarbons by extraction from the hydrocarbon mixture from which light matters have been removed. The hydrocarbon oil for hydrogen production stably has a high degree of desulfurization and enables a reformer to have excellent durability. It gives reformed gases reduced in carbon monoxide content and has a high hydrogen generation efficiency.

Description

Hydrocarbon oil for hydrogen production and hydrogen production system

[Technical field]

The present invention relates to a hydrocarbon oil for hydrogen production and a hydrogen production system. [Background technology]

In recent years, the growing sense of danger to the global environment in the future has required the development of an energy-friendly energy supply system that is friendly to the earth. Fuel cells, hydrogen Hydrogen-fueled systems such as rice fields are in the limelight, among which hydrogen is supplied directly to the fuel cell by compression or liquefaction, as well as methanol. There is known a method of supplying oxygen-containing fuel such as naphtha, kerosene, and other hydrocarbons by reforming hydrocarbons (see, for example, Non-Patent Document 1). Although it has the advantage of being able to be used as a gas, it has problems in storage properties because it is a gas at room temperature, and in its mountability when used in vehicles, etc. Methanol is used to convert hydrogen by reforming in the system. Although it is relatively easy to manufacture, it has low energy efficiency per weight, is toxic and corrosive, and has difficulties in handling and storage properties. Hydrogen production has attracted attention due to the fact that existing fuel supply infrastructure can be used, the overall energy efficiency is high, etc. The sulfur content in these hydrocarbons is used in the reforming process to generate hydrogen. It is generally known that the catalyst used and the performance of a fuel cell, particularly a polymer electrolyte fuel cell, are degraded. In general, the operating pressure of a fuel cell system is set to normal pressure (large) due to reasons such as installation of stationary fuel cells in homes and commercial areas. However, in the desulfurization process near normal pressure (atmospheric pressure), stable and sufficient desulfurization efficiency may not be obtained depending on the type of hydrocarbon. Such hydrocarbons require a reforming process for hydrogen generation, but there are problems with the durability of the reforming system and high hydrogen generation efficiency may not be obtained. It was. When hydrocarbons are further reformed, carbon monoxide, carbon dioxide, methane, etc. are included in the reformed gas in addition to hydrogen. It is known that carbon monoxide in the reformed gas is a catalyst poison that lowers the performance of a catalyst contained in an electrode used in a fuel cell, particularly a polymer electrolyte fuel cell. For this reason, carbon monoxide purifiers are installed in fuel cells that use hydrocarbons, especially in hydrogen production systems for polymer electrolyte fuel cells. However, depending on the type of hydrocarbon, the amount of carbon monoxide generated in the reformed gas was large, and high hydrogen generation efficiency could not be obtained.

(Non-Patent Document 1) Masao Ikematsu, "Engine Technology", Sankaidosha, 2001

January, Volume 3, Issue 1, p. 35

[Disclosure of the Invention]

In view of such circumstances, the present invention provides a stable and high desulfurization rate, excellent durability of the reformer, a low amount of carbon monoxide generated in the reformed gas, and high hydrogen generation efficiency. The purpose is to provide a production hydrocarbon oil and hydrogen production system.

As a result of intensive studies, the present inventors have found that a hydrocarbon oil having a specific property obtained by treating a specific raw material in a specific step can solve the above problems, and have completed the present invention. That is, in the first aspect of the present invention, the initial boiling point is 140 to 180 ° C., 90% by volume, the distillation temperature is 200 to 270 ° C., and the aromatic content is 20% by volume. Hereinafter, the content of the linear saturated hydrocarbon is 25 mass. /. As described above, a hydrocarbon mixture having a linear saturated hydrocarbon content of 10 to 15 carbon atoms of 20% by mass or more and a sulfur content of 300% by mass or less is used as a raw material oil, and the following step (1) (3) containing a hydrocarbon base material, having an initial boiling point of 160 ° C. or more and 200 ° C. or less, and a 50% by volume distillation temperature of 200 ° C. or more 2 20 ° C or less, 90% by volume Distillation temperature: 220 ° C or more, 245 ° C or less, aromatic content: 10% by volume or less, sulfur content: 0.5 mass ppm or less, naphthene content Hydrogen production with at least a desulfurization reactor, characterized in that at least 40% by volume, oxidation start temperature is at least 210 ° C, and the ratio of hydrocarbons having 13 carbon atoms is at least 20% by mass. The system relates to hydrocarbon oils for hydrogen production. Step (1):.. Feedstock oil, a reaction temperature two hundred and fifty to three hundred ten ° C, the hydrogen pressure 5~1 OMP a, LHSV 0. 5~3 0 h 1, hydrogen Z hydrocarbon volume ratio 0.1 5-0 6 Selected from Ni—W, Ni—Mo, Co—Mo, Co—W, and Ni—Co—Mo under the following conditions: Process

Step (2): Stripping 1 to 35% by volume of light components from the hydrodesulfurized oil obtained in Step (1)

Step (3): After stripping the light components, extracting and removing 10% by volume or more of the linear saturated hydrocarbon with zeolite under the conditions of a temperature of 150 to 250 ° C and a pressure of 1 to 5 MPa. The second is that the initial boiling point is 140 to 180 ° C, the 90% by volume distillation temperature is 200 to 270 ° C, the aromatic content is 20% by volume or less, and the linear saturated hydrocarbon content is 25% by mass or more. Using a hydrocarbon mixture having a linear saturated hydrocarbon content of 10 to 15 carbon atoms of 20% by mass or more and a sulfur content of 300% by mass or less as a feedstock oil, the following steps (1) to (4) The resulting hydrocarbon base material contains a 95% by volume distillation temperature of 240 ° C or less, a difference between the 95% by volume distillation temperature and the initial boiling point of 50 ° C or less, and a sulfur content of 0.5%. Mass: ppm or less, molar ratio of carbon to hydrogen: 1.95 or more, naphthene content: 40% by volume or more, aromatics: 10% by volume or less, oxidation start temperature: 210 ° C or more It features relating to hydrogen production hydrocarbon oil of the hydrogen production system disposed at least carbon monoxide purifier to.

Step (1):.. Feedstock oil, a reaction temperature two hundred and fifty to three hundred ten ° C, the hydrogen pressure 5~1 OMP a, LHSV 0. 5~3 0 h 1, hydrogen Z hydrocarbon volume ratio 0.1 5-0 6 Hydrodesulfurization treatment with a catalyst selected from Ni-W, Ni-Mo, Co-Mo, Co-W, and Ni-Co-Mo under the following conditions: Process

Step (2): Step of stripping 1 to 35% by volume of light components from the hydrodesulfurized oil obtained in Step (1)

Step (3): After stripping the light components, extracting and removing 10% by volume or more of linear saturated hydrocarbons by zeolite under the conditions of a temperature of 150 to 250 ° C and a pressure of 1 to 5 MPa.

Step (4): fractionate the hydrocarbon oil from which the straight-chain saturated hydrocarbon has been extracted and removed in step (3) In the third step of the present invention, the initial boiling point is 140 to 180 ° C., the 90% by volume distillation temperature is 200 to 270 ° C., the aromatic content is 20% by volume or less, and the linear saturated hydrocarbon is contained. A hydrocarbon mixture having an amount of 25% by mass or more, a straight-chain saturated hydrocarbon having 10 to 15 carbon atoms of 20% by mass or more, and a sulfur content of 300% by mass or less is used as a raw material oil in the following step ( 1) to (3) and (5) containing a hydrocarbon base material, flash point of 40 ° C or higher, initial boiling point of 145 ° C or higher, 170 ° C or lower, 50% by volume Distillation temperature: 180 ° C to 220 ° C, 95% by volume Distillation temperature: 220 ° C to 260 ° C, Sulfur content 0.5 mass ppm or less, Smoke point 26 mm or more, Aromatic The present invention relates to a hydrocarbon oil for hydrogen production in a hydrogen production system having at least a reformer, wherein the content is 10% by volume or less and the oxidation start temperature is 210 ° C. or more.

Step (1): Feed oil at a reaction temperature of 250 to 310 ° C, hydrogen pressure of 5 to ¹ OMPa, LHSV of 0.5 to 3.0 h— ¹ , hydrogen / hydrocarbon capacity ratio of 0.15 to 0 Under the conditions of 6, hydrogenation with a catalyst containing one selected from Ni—W, Ni—Mo, Co—Mo, Co—W, and Ni_Co—Mo power Desulfurization process

Step (3): After stripping the light components, extracting and removing 10% by volume or more of linear saturated hydrocarbons with zeolite under conditions of a temperature of 150 to 250 ° C and a pressure of 1 to 5 MPa.

Step (5): The hydrocarbon obtained in Step (3) or the hydrocarbon obtained in Step (4) is fractionated with the hydrocarbon obtained in Step (3). A step of mixing 60% by volume or more of the light component stripped in the fourth step of the present invention is to mix the first hydrocarbon oil of the present invention with a reaction pressure (absolute pressure) IMPa of a desulfurization reactor, Hydrogen equipped with a desulfurization reactor for desulfurization by controlling the maximum temperature of the desulfurization catalyst layer in the range of the initial boiling point of hydrocarbon oil-50 ° C to the initial boiling point of hydrocarbon oil + 100 ° C Related to manufacturing system.

A fifth aspect of the present invention is that a reformed gas obtained by reforming the second hydrocarbon oil of the present invention and water The reaction temperature is adjusted to 100 to 6 in the presence of a catalyst containing an active metal containing one or more elements selected from Groups IB, IIB, VI, and VIII of the Periodic Table by mixing steam. Water gas shift reactor for obtaining carbon dioxide and hydrogen as products from carbon monoxide and water vapor at a temperature of 00 ° C and a ratio of water to carbon monoxide in reformed gas of 1 to 80 mol / mol It relates to a hydrogen production system.

A sixth aspect of the present invention is directed to a sixth aspect of the present invention, in which a mixed gas of the third hydrocarbon oil and the steam of the third aspect of the present invention is used in the presence of a reforming catalyst containing a Group VIII element of the periodic table as an active metal, at a reaction temperature of 400 to 1 A hydrogen production system equipped with a steam reforming reformer that obtains a product containing hydrogen as a main component by reacting at 00 ° C. and a mixing ratio of water and hydrocarbon oil of 1 to 5 mol Z mol. About

A seventh aspect of the present invention is to provide a mixed gas of the third hydrocarbon oil, steam and air of the present invention in the presence of a reforming catalyst containing a Group VIII element of the periodic table as an active metal, at a reaction temperature of 400. 1100 ° (: The reaction is carried out at a mixing ratio of water and hydrocarbon oil of 0.5 to 5 mol Z mol and a mixing ratio of oxygen and hydrocarbon oil of 0.1 to 0.5 mol Z mol. Accordingly, the present invention relates to a hydrogen production system equipped with an autothermal reformer for obtaining a product containing hydrogen as a main component.

An eighth aspect of the present invention relates to the above-described hydrogen production system, comprising a desulfurization reactor, a reformer, and a carbon monoxide purifier. Hereinafter, the present invention will be described in detail.

The hydrocarbon oil for hydrogen production of the present invention is a hydrocarbon oil having a specific property, comprising a hydrocarbon base material obtained by using a specific hydrocarbon mixture as a raw material oil and treating it in a specific step. It is.

The hydrocarbon mixture used as the starting material oil has an initial boiling point of 140-180 ° C, 90% by volume, a distillation temperature of 200-270 ° C, and an aromatic content of 20% by volume. % Or less, straight-chain saturated hydrocarbon content is 25% by mass or more, straight-chain saturated hydrocarbon having 10 to 15 carbon atoms is 20% by mass or more, and sulfur content is 300% by mass or less. It is necessary to be. Preferably, the initial boiling point is 150-170 ° C, 90 vol% distilling temperature is 222-245 ° C, the aromatic content is 15 vol% or less, and linear saturation. Hydrocarbon content is 35% by volume or more, linear saturated hydrocarbons having 10 to 15 carbon atoms is 25% by volume or more, and sulfur content is 20% by volume. 0 mass p pm or less. If the properties of the feed oil are out of the above range, it is not preferable because the hydrocarbon oil of the present invention is difficult to obtain.

Here, the initial boiling point and 90% by volume distillation temperature are based on JIS K2254 “Petroleum product one distillation test method-Normal pressure distillation test method”, and the aromatic content is JIS K253 6 “Petroleum product one hydrocarbon type The values measured by the fluorescent indicator adsorption method, the content of straight-chain saturated hydrocarbons, and the content of straight-chain saturated hydrocarbons having 10 to 15 carbon atoms in “Test method” are the values measured using GC-FID (mass %). In other words, a methyl silicon capillary column (ULTRAALLOY-1) is used as the column, helium is used as the carrier gas, and a hydrogen ion detector (FID) is used as the detector. Column length is 30 m, carrier gas flow is 1.0 mLZm. in, split ratio 1:79, sample injection temperature 360 ° C, column heating condition 140 ° C → (8 ° C / min) → 355 ° C, value measured under the condition of detector temperature 360 ° C It is. The sulfur content is a value measured by JIS K2541 "Crude oil and petroleum products-Sulfur content test method". The feedstock is processed in the following steps (1) to (3).

In step (1), the feedstock is subjected to a reaction temperature of 250 to 310 ° C, a hydrogen pressure of 5 to 10 MPa, an LHSV of 0.5 to 3.0 h- ¹ , a hydrogen Z hydrocarbon volume ratio of 0. Hydrogenation with a catalyst containing any one selected from Ni-W, Ni-Mo, Co-Mo, Co-W, and Ni-Co_Mo under the conditions of 15 to 0.6 The desulfurization treatment is performed, and the reaction temperature of the hydrodesulfurization treatment is from 250 to 310 ° C, and preferably from 28 to 300 ° C. If the reaction temperature is lower than 250 ° C, a sufficient hydrodesulfurization reaction rate cannot be obtained, while if it exceeds 310 ° C, the hydrodesulfurization reaction becomes insufficient in terms of reaction equilibrium.

The hydrogen pressure in the hydrodesulfurization treatment is 5 to 10 MPa, preferably 7 to 9 MPa.

The LHSV in the hydrodesulfurization treatment is 0.5 to 3.0 h- ¹ , preferably 1-2 h- ¹ . LHSV Although it is advantageous for as low reaction, the case of less than 0. 5 h one ¹ requires a very large reactor volumes.

The hydrogen / hydrocarbon capacity ratio is 0.15 to 0.6, preferably 0.2 to 0.6. 0.4.

When the hydrogen pressure is less than 5 MPa or when the hydrogen-Z hydrocarbon volume ratio is less than 0.15, the effect of promoting the desulfurization reaction or the hydrogenation reaction becomes insufficient. If the hydrogen pressure exceeds 1 OMPa, or if the hydrogen / "hydrocarbon capacity ratio exceeds 0.6, the equipment cost increases.

The catalyst used in the hydrodesulfurization treatment contains any active metal selected from Ni-W, Ni-Mo, Co_Mo, Co-W, and Ni-Co-Mo. It is necessary. The active metal is preferably used by being supported on a porous carrier. As the porous carrier, an inorganic oxide is preferably used. Specific examples of the inorganic oxide include alumina, titania, zirconia, polya, silica, and zeolite.Of these, at least one of titania, zirconia, polya, silica, and zeolite is composed of alumina. Are suitably used in the present invention. The amount of the active metal to be supported is not particularly limited, but is preferably 20 to 35% by mass in total of the metal oxide based on the total amount of the catalyst.

The catalyst is preferably used after pre-sulfidation treatment with hydrogen and sulfur compounds. In general, a gas containing hydrogen and sulfur compounds is circulated, and the active metal on the catalyst is pre-sulfided by applying heat of 200 ° C or more according to a predetermined procedure, and hydrogenation and desulfurization activities are exhibited. Will be. In step (2), light components (generally a boiling point of 200 ° C or less) are stripped (removed) from the hydrodesulfurized oil obtained in step (1). The strip amount is 1 to 35% by volume, preferably 10 to 35% by volume, and more preferably 20 to 35% by volume, based on the hydrodesulfurized oil. If stripping is not performed, or if the stripping amount is not sufficient, the load on the subsequent straight-chain saturated hydrocarbon removal device will increase, and the removal efficiency will decrease. On the other hand, if the strip amount is excessive (more than 35% by volume), the time required for the strip treatment increases, which is not preferable. In step (3), the hydrocarbon oil from which the light components have been stripped (removed) in step (2) is subjected to a temperature of 150 ° C to 250 ° C and a pressure of 1 to 5 MPa. Extract and remove 10% by volume or more of straight-chain saturated hydrocarbons with zeolite. The extraction temperature for the removal of linear saturated hydrocarbons is 150 ° (: ~ 250 ° C, preferably 180-200 ° C. If the extraction temperature is below 150 ° C, sufficient linear saturation The removal rate of hydrocarbons cannot be obtained On the other hand, if the temperature exceeds 250 ° C, the efficiency of removing saturated Naugagu hydrocarbons decreases, and the pressure at this time is 1 to 5 MPa, preferably 1.5 If the pressure is less than IMPa, a sufficient removal rate of linear saturated hydrocarbons cannot be obtained, whereas if the pressure exceeds 5 MPa, a sufficient removal rate of linear saturated hydrocarbons can be obtained. The zeolite used for removing the linear saturated hydrocarbon is not particularly limited, but generally A-type zeolite is used, among which molecular sieve 5A is preferable. It is preferable to extract and remove hydrogen by 10% by volume or more, preferably 20% by volume or more. The hydrocarbon oil (I) of the invention is a hydrocarbon oil having the following specific properties, comprising the above-mentioned starting material oil and a hydrocarbon base material obtained through steps (1) to (3). .

The lower limit of the initial boiling point (I BP) of the hydrocarbon oil (I) of the present invention must be 160 ° C or higher, and preferably 170 ° C or higher, in order to obtain a stable and high desulfurization rate. 180 ° C or higher is more preferable. On the other hand, the upper limit needs to be 200 ° C or lower, and preferably 190 ° C or lower, from the viewpoint of the startability of the desulfurization system.

The lower limit of the 50% by volume distilling temperature (T50) of the hydrocarbon oil (I) of the present invention must be 200 ° C or higher in order to obtain a stable and high desulfurization rate. Above is preferable, and 210 ° C. or higher is more preferable. On the other hand, the upper limit needs to be 220 ° C or lower from the viewpoint of the desirability of the desulfurization system.

From the viewpoint of the durability of the desulfurization system, the lower limit of the 90% by volume distillation temperature (T 90) of the hydrocarbon oil (I) of the present invention must be 220 ° C. or higher, and 225 ° C. or lower. Above is preferable, and 230 ° C or more is more preferable. On the other hand, the upper limit needs to be 245 ° C or lower, and preferably 240 ° C or lower, because the hydrocarbon component in the reformed gas at the time of the reforming reaction increases.

The distillation properties of the hydrocarbon oil (I) of the present invention other than IBP, T50 and 、 90 are not particularly limited, but the 10% by volume distillation temperature (Τ10) is from 170 ° C to 220 ° C. Is preferred. The lower limit of T 10 is 1 8 because evaporation gas (THC) is likely to be generated. It is more preferably 0 ° C or higher, further preferably 190 ° C or higher, and most preferably 195 ° C or higher. On the other hand, from the viewpoint of the startability of the desulfurization system, the temperature is preferably 210 ° C or lower, more preferably 200 ° C or lower.

The end point (EP) is preferably from 230 ° C to 280 ° C. From the viewpoint of the durability of the desulfurization system, the temperature is preferably 240 ° C or higher, more preferably 250 ° C or higher. From the viewpoint of the startability of the desulfurization system, the temperature is preferably 270 ° C or lower, more preferably 260 ° C or lower.

Note that IBP, T10, Τ50, Τ90 and EP here are JISK2

254 This is a value measured by “Petroleum product single distillation test method-normal pressure distillation test method”.

The aromatic content of the hydrocarbon oil (I) of the present invention must be 10% by volume or less from the viewpoint of a decrease in the desulfurization rate and a decrease in the durability of the desulfurization system, and is 8 volumes. / ₀ or less is preferred.

The olefin content of the hydrocarbon oil (I) of the present invention is not particularly limited, but is preferably 5% by volume or less, more preferably 1% by volume or less, from the viewpoint of the durability of the desulfurization system. Most preferably, 1% by volume or less.

The saturated content of the hydrocarbon oil (I) of the present invention is not particularly limited, but is preferably 85% by volume or more, more preferably 90% by volume or more, in view of the short start-up time of the desulfurization system.

The aromatic content, olefin content and saturated content described above are the aromatic content, olefin content, and saturated hydrocarbon content measured by the fluorescent indicator adsorption method of JISK 2536 “Petroleum product-hydrocarbon type test method”. The value of the quantity.

The sulfur content of the hydrocarbon oil (I) of the present invention must be 0.5 mass ppm or less in view of the desulfurization rate and the durability of the desulfurization catalyst, and is preferably 0.3 mass ppm or less. Preferably, 0.2 quality * ppm or less is more preferable.

Here, the sulfur content is a value measured by ASTM D4045-96 "Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric ColorimetryJ. (See comments on page 5.)

The naphthene content of the hydrocarbon oil (I) of the present invention needs to be 40% by volume or more from the viewpoint of reducing the desulfurization rate and suppressing the decrease in the durability of the desulfurization catalyst. preferable.

The naphthene content here refers to the content of naphthenic hydrocarbons measured by a method in accordance with ASTM D2425 (Test Method for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants). It is about quantity.

The oxidation start temperature of the hydrocarbon oil (I) of the present invention needs to be 210 ° C. or higher, preferably 212 ° C. or higher, more preferably 215 ° C. or higher. . If the oxidation start temperature is lower than 210 ° C., it is not preferable because the durability of the desulfurization system deteriorates due to coking of the catalyst.

The oxidation start temperature in the present invention is measured by using a high-pressure differential scanning calorimeter (hereinafter, referred to as “high-pressure DSC”). More specifically, the sample is introduced into a DSC pressurized cell (for example, manufactured by Metrado Red), and the sample is subjected to 20 ° C / min from 30 ° C to 500 ° C under an air atmosphere of 4 MPa. As a result, a correlation curve between the calorific value and the temperature is obtained. The oxidation start temperature is determined based on the force and the exothermic peak that appears first in the correlation curve.

Fig. 1 is a graph showing an example of a correlation curve between the calorific value and the temperature measured using a high-pressure DSC, and shows the measurement results for a hydrocarbon oil (I-A) described later. In Fig. 1, the vertical axis is the calorific value, and the horizontal axis is the temperature. FIG. 2 is a graph showing a derivative curve of the curve shown in FIG. In FIG. 1, the straight line 1 shows the tangent at the point where the heat generation per unit time is the maximum (point corresponding to point B in FIG. 2). Also, 1 ₂ in Figure 1 illustrates a tangent line at the start of the heating (point curve rises). The temperature corresponding to the intersection A between 1 and ₁₂ is the oxidation start temperature specified in the present invention.

The component ratio of the hydrocarbon having 13 carbon atoms in the hydrocarbon oil (I) of the present invention is 20 mass from the viewpoint of the durability of the desulfurization system. / ₀ or more, preferably 25% by mass or more.

Here, the number 1 3 in hydrocarbon content of carbon is a value (mass ^_0/0) which is determined using GC-FID. In other words, the column is a methyl silicon capillary column (ULTRAAL LOY-1, 0.25 mm φ, 30 m), and the carrier gas is Using a hydrogen ion detector (FID) as the detector, the carrier gas flow rate is 1. OmL / min, the split ratio is 1:79, the sample injection temperature is 280 ° C, and the column temperature is 50 ° C (5 minutes) → (5 ° C / min) → 280 ° C (10 minutes), the value obtained by integrating the area of hydrocarbons with 13 carbon atoms by chromatography measured under the conditions of a detector temperature of 300 ° C.

As the hydrocarbon oil (I) of the present invention, a hydrocarbon base material obtained through the aforementioned steps (1) to (3) can be used. In addition, another base material can be appropriately mixed with the hydrocarbon base material as long as the above properties are maintained. The mixing ratio of the other base materials that can be mixed is preferably 20% by volume or less, more preferably 15% by volume or less, and more preferably 10% by volume or less based on the total amount of the hydrocarbon oil. Preferred. If the content of the other base material exceeds 20% by volume, it is not preferable from the viewpoint of deteriorating the durability of the desulfurization catalyst. In the second aspect of the present invention, as a step (4), the hydrocarbon mixture from which the straight-chain saturated hydrocarbons have been extracted and removed in the step (3) is fractionated by a distillation operation. The cut point in the fractionation is that the hydrocarbon base material generated by this operation has a 95% by volume distillation temperature of 240 ° C or less, and the difference between the 95% by volume distillation temperature and the initial boiling point is 50 ° C. Control to be below C. It is desirable to install a hydrogenation unit before distillation to reduce the aromatic content of the product.

The hydrocarbon oil for hydrogen production (Π) of the present invention is a hydrocarbon having the following specific properties, comprising the above-mentioned starting material oil and a hydrocarbon base obtained through steps (1) to (4). Oil.

The upper limit of the 95% by volume distilling temperature (T 95) of the hydrocarbon oil (本) of the present invention is determined from the viewpoint of low carbon monoxide generation in reformed gas and high hydrogen generation efficiency. It is necessary to be not more than ° C, preferably not more than 220 ° C, and more preferably not more than 180 ° C.

The difference between the 95% by volume distillation temperature (T 95) and the initial boiling point (I BP) of the hydrocarbon oil (Π) of the present invention is due to the low carbon monoxide generation amount in the reformed gas and the hydrogen generation efficiency From the viewpoint of height, the temperature must be 50 ° C or lower, preferably 40 ° C or lower, more preferably 15 ° C or lower. Further, the distillation properties of the hydrocarbon oil (Π) other than T95 of the present invention are not particularly limited, but it is necessary for the IBP so that the difference between T95 and IBP satisfies the above-mentioned specific range.

IBP is preferably 145 ° C or higher, more preferably 150 ° C or higher, and most preferably 155 ° C or higher, from the viewpoints of flammability, increase in evaporative gas (THC), and handleability. On the other hand, from the viewpoint of deteriorating the start-up time of the hydrogen production system, the temperature is preferably 220 ° C. or lower, more preferably 205 ° C. or lower, and most preferably 170 ° C. or lower.

The 10% by volume distillation temperature (T 10) is preferably from 150 ° C to 220 ° C. From the viewpoint of flammability and an increase in evaporative gas (THC), the temperature is more preferably at least 155 ° C, and even more preferably at least 160 ° C. On the other hand, from the viewpoint of deteriorating the start-up time of the hydrogen production system, the temperature is preferably 210 ° C or lower, and more preferably 180 ° C or lower.

The 50% by volume distillation temperature (T 50) is preferably from 150 ° C to 220 ° C. From the viewpoint of the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide generated, the temperature is more preferably 155 ° C or higher, and further preferably 160 ° C or higher. On the other hand, the temperature is more preferably 210 ° C. or lower, and further preferably 180 ° C. or lower, from the viewpoint of deterioration of the starting time of the hydrogen production system.

The 90% by volume distillation temperature (T90) is preferably from 160 ° C to 250 ° C. From the viewpoint of the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide generated, the temperature is more preferably 165 ° C or higher, and further preferably 170 ° C or higher. On the other hand, from the viewpoint of an increase in THC in the exhaust gas, the temperature is more preferably 220 ° C or lower, and further preferably 180 ° C or lower.

The end point (EP) is preferably from 160 ° C to 260 ° C. From the viewpoint of the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide generated, the temperature is more preferably 170 ° C or higher, and further preferably 180 ° C or higher. On the other hand, from the viewpoint of increasing THC in the exhaust gas, the temperature is more preferably 230 ° C or lower, and further preferably 210 ° C or lower.

Here, いう ΒΡ, Τ 10, Τ 50, Τ 90, Τ 95, and ぴ、 are J

IS No. 2254 This is a value measured by “Petroleum product single distillation test method-atmospheric pressure distillation test method”. The sulfur content of the hydrocarbon oil (Π) of the present invention depends on the desulfurization rate, the durability of the desulfurization catalyst, the durability of the reforming catalyst, the lowering of the reforming reactivity, and the amount of hydrogen generated per carbon dioxide generated. Therefore, it is necessary to be 0.5 mass ppm or less, preferably 0.3 mass ppm or less, more preferably 0.15 mass ppm or less.

Here, the sulfur content is a value measured by ASTM D4045-96 “Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric ColorimetryJ”.

The hydrocarbon oil (II) of the present invention requires that the molar ratio of carbon to hydrogen (CZH) in the hydrocarbon oil be 1.95 or more. From the viewpoint of the small amount of carbon monoxide generated in the reformed gas and the high hydrogen generation efficiency, 2.00 or more is preferable, and 2.05 or more is more preferable.

The molar ratio of carbon to hydrogen in hydrocarbon oil (CZH) is measured by a method based on ASTM D 5291-01 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry). Value. The naphthene content of the hydrocarbon oil (Π) of the present invention is determined to be lower in desulfurization rate, lower in durability of desulfurization catalyst, lower in durability of reforming catalyst, lower in reforming reactivity, lower in carbon monoxide purification catalyst. It is necessary to be at least 40% by volume, preferably at least 45% by volume, from the viewpoint of suppressing the reduction of the durability of carbon dioxide, the reduction of the carbon monoxide removal rate, and the reduction of the amount of hydrogen generated per amount of carbon dioxide generated. , 50% by volume or more is more preferable.

The naphthenic content referred to here is the naphthenic hydrocarbon content measured by a method based on ASTM D 2425 (Test Method for Instrumental Determination of arbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants). Say.

The aromatic hydrocarbon content of the hydrocarbon oil (II) of the present invention is as follows: decrease in desulfurization rate, decrease in durability of desulfurization catalyst, decrease in durability of reforming catalyst, decrease in reforming reactivity, reduction in monoxide. It is necessary to be 10% by volume or less from the viewpoint of suppressing the reduction of the durability of the carbon purification catalyst, the reduction rate of carbon monoxide, the reduction of the amount of hydrogen generated per amount of carbon dioxide, etc., and 5% by volume. Or less, more preferably 3% by volume or less, still more preferably 1% by volume or less, and even more preferably 0.5% by volume or less.

There is no restriction on the olefin content of the hydrocarbon oil (炭化) of the present invention, It is preferably 5% by volume or less, more preferably 1% by volume or less, and 0.3% by volume, from the viewpoints of low deterioration of the quality catalyst, long-lasting initial performance and good storage stability. The following are most preferred.

The saturated hydrocarbon content of the hydrocarbon oil (Π) of the present invention is not limited at all, but the amount of hydrogen generated per weight, the amount of hydrogen generated per carbon dioxide, and the amount of exhaust gas From the viewpoints of low THC and short system startup time, 85% by volume or more is preferable, 90% by volume or more is more preferable, and 95% by volume or more is most preferable.

The above-mentioned aromatic content, olefin content, and saturated hydrocarbon content are values measured by the fluorescent indicator adsorption method of JIS K 253 “Petroleum products—one hydrocarbon type test method”.

The oxidation start temperature of the hydrocarbon oil (Π) of the present invention needs to be 210 ° C. or higher, preferably 212 ° C. or higher, more preferably 215 ° C. or higher. . If the oxidation start temperature is lower than 210 ° C., it is not preferable because the coking of the reforming catalyst deteriorates the durability of the hydrogen production apparatus.

As the hydrocarbon oil (II) for hydrogen production of the present invention, a hydrocarbon base material obtained through the aforementioned steps (1) to (4) can be used. Further, other hydrocarbon-producing substrates may be appropriately mixed with the hydrocarbon substrate as long as the above properties are maintained. The mixing ratio of other base materials that can be mixed is preferably 20% by volume or less, more preferably 15% by volume or less, and more preferably 10% by volume or less based on the total amount of the hydrocarbon oil. More preferred. If the content of the other base material exceeds 20% by volume, the amount of hydrogen generated per weight decreases, and the amount of carbon dioxide generated per hydrogen generation is undesirably increased. In the third aspect of the present invention, after the above-mentioned steps (.1) to (3), as a step (5), the hydrocarbon obtained in the step (3) or the hydrocarbon obtained in the step (4) Then, 60% by volume or more, preferably 70% by volume or more, of the light components stripped in step (2) is mixed.

The hydrocarbon oil (ΙΠ) for hydrogen production of the present invention contains a hydrocarbon base obtained by subjecting the above-mentioned starting material oil to the steps (1) to (3) and (5). Specificity It is a hydrocarbon oil having a shape.

The flash point of the hydrocarbon oil (m) of the present invention must be 4 ° C or higher, preferably 42 ° C or higher, more preferably 45 ° C or higher, from the viewpoints of flammability and easy handling. Better.

The flash point here is a value measured by JIS K 2265 "Crude oil and petroleum products-Flash point test method".

The lower limit of the initial boiling point (I BP) of the hydrocarbon oil (II) of the present invention needs to be 145 ° C or higher, preferably 150 ° C or higher. On the other hand, the upper limit needs to be 170 ° C. or lower, preferably 165 ° C. or lower, more preferably 160 ° C. or lower, and even more preferably 150 ° C. or lower. If I BP is lower than 145 ° C, it is not preferable from the viewpoint of flammability, increase in evaporative gas (THC), and handleability. If I BP exceeds 165 ° C, it is not preferable because the start-up time of the hydrogen production system deteriorates.

The lower limit of the 50% by volume distillation temperature (T 50) of the hydrocarbon oil (m) of the present invention needs to be 18 ° C. or higher, preferably 185 ° C. or higher, and more preferably 190 ° C. or higher. More preferred. On the other hand, the upper limit needs to be 220 ° C or lower, preferably 215 ° C or lower, more preferably 210 ° C or lower. If T50 is lower than 180 ° C, the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide decrease, which is not preferable.If it exceeds 220 ° C, it is preferable because the start-up time of the hydrogen production system deteriorates. Absent. The lower limit of the 95% by volume distillation temperature (T95) of the hydrocarbon oil (ΙΠ) of the present invention needs to be 220 ° C or higher, preferably 225 ° C or higher, more preferably 230 ° C or higher. Good. On the other hand, the upper limit needs to be 260 ° C or lower, preferably 255 ° C or lower, and more preferably 250 ° C or lower. If T95 is lower than 220 ° C, the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide decrease, which is not preferable.If it exceeds 260 ° C, THC in exhaust gas increases, which is not preferable. .

The distillation properties of the hydrocarbon oil (ΙΠ) of the present invention other than IBP, T50 and Τ95 are not particularly limited, but the 10% by volume distillation temperature (Τ10) is from 160 ° C to 190 ° C. preferable. The temperature is more preferably 165 ° C or more, and further preferably 170 ° C or more, because the flammability is increased and evaporative gas (THC) is easily generated. On the other hand, the temperature is preferably 185 ° C or less, more preferably 180 ° C or less, because of the deterioration of the start-up time of the hydrogen production system. The 90% by volume distillation temperature (T 90) is preferably from 210 ° C to 255 ° C. Since the amount of hydrogen generation per weight and the amount of hydrogen generation per carbon dioxide generation decrease, 220 ° C or higher is more preferable, and 230 ° C or higher is more preferable. On the other hand, since THC in the exhaust gas increases, the temperature is preferably 245 ° C or lower, and more preferably 240 ° C or lower.

The end point (EP) is preferably from 230 ° C to 280 ° C. 240 ° C. or higher is more preferable, and 245 ° C. or higher is more preferable because the amount of hydrogen generation per weight and the amount of hydrogen generation per carbon dioxide generation decrease. On the other hand, since THC in the exhaust gas increases, the temperature is preferably 270 ° C or lower, more preferably 260 ° C or lower.

Note that Ι ΒΡ, Τ 10, Τ 50, Τ 90, Τ 95, and いう Ρ here are the values measured by JIS Κ 2254 `` Petroleum products-one distillation test method-normal pressure distillation test method ''. .

The sulfur content of the hydrocarbon oil (m) of the present invention is 0 from the viewpoint of the desulfurization rate, the durability of the desulfurization catalyst, the durability of the reforming catalyst, the decrease in the reforming reactivity, and the amount of hydrogen generated per carbon dioxide generated. It is necessary to be not more than 5 mass ppm, preferably not more than 0.3 mass ppm, more preferably not more than 0.2 mass ppm.

Here, the sulfur content is a value measured by ASTM D4045-96 “Standard Test Method for Sulfur in Petroleum Products by Hydrogenesis and Rateometric ColorimetryJ”.

The smoke point of the hydrocarbon oil (m) of the present invention is that the amount of hydrogen generated per weight is large, the amount of hydrogen generated per carbon dioxide is large, the THC in exhaust gas is small, 26 mm or more is necessary, 27 mm or more is preferable, and 28 mm or more is more preferable because the starting time is short, the deterioration of the reforming catalyst is small, and the initial performance can be maintained for a long time.

The smoke point is a value measured by JIS K2537 "Test method for petroleum products-kerosene and aviation turbine fuel oil-smoke point".

The aromatic content of the hydrocarbon oil (ΙΠ) of the present invention is that the amount of hydrogen generated per weight is large, the amount of hydrogen generated per carbon dioxide is large, the THC in exhaust gas is small, From the viewpoint that the system startup time is short, the deterioration of the reforming catalyst is small, and the initial performance can be maintained for a long time, the content must be 10% by volume or less. % By volume or less is preferred.

There is no limitation on the olefin content of the hydrocarbon oil (m) of the present invention. However, the amount of hydrogen generated per weight is large, the amount of hydrogen generated per carbon dioxide is large, and the THC in the exhaust gas is high. 5% by volume or less, preferably 1% by volume, from the viewpoints that the amount of the catalyst is small, the system startup time is short, the deterioration of the reforming catalyst is small, the initial performance can be maintained for a long time, and the storage stability is good. The lower limit is more preferably 0.5% by volume or less.

The saturated hydrocarbon content (total amount of saturated and naphthenic components) of the hydrocarbon oil (m) of the present invention is not limited at all, but the amount of hydrogen generated per weight is large, and the amount of hydrogen per carbon dioxide generated is large. From the viewpoints of a large amount of generation, a small amount of THC in the exhaust gas, and a short system startup time, it is preferably 85% by volume or more, more preferably 90% by volume or more, and 95% by volume or more. The above is most preferred.

The hydrocarbon oil of the present invention (the naphthenic hydrocarbon content of mo is not limited at all. However, when the content of the naphthenic hydrocarbon decreases, the desulfurization rate decreases, the durability of the desulfurization catalyst decreases, and the reforming catalyst decreases. It is preferably at least 30% by volume, more preferably at least 40% by volume, from the viewpoint of suppressing the reduction of the durability of the steel, the reduction of the reforming reactivity, and the reduction of the amount of hydrogen generated per amount of carbon dioxide. It is more preferably at least 45% by volume.

Here, the content of the naphthenic hydrocarbon is measured by a method based on ASTM D2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry).

The oxidation initiation temperature of the hydrocarbon oil (II) of the present invention needs to be 210 ° C. or higher, preferably 212 ° C. or higher, more preferably 215 ° C. or higher. If the oxidation start temperature is lower than 210 ° C., it is not preferable in that the coking of the reforming catalyst deteriorates the durability of the hydrogen production apparatus.

As the hydrocarbon oil (II) of the present invention, a hydrocarbon base material obtained through the aforementioned steps (1) to (3) and (5) can be used. Further, another hydrocarbon-producing base material may be appropriately mixed with the hydrocarbon base material within a range in which the above properties are maintained. You can also. The mixing ratio of the other base materials that can be mixed is preferably 20% by volume or less, more preferably 15% by volume / ₀ or less, and more preferably 10% by volume or less, based on the total amount of the hydrocarbon oil. Is more preferable. If the content of the other base material exceeds 20% by volume, it is not preferable in terms of a decrease in the conversion to a hydrogen-rich reformed gas at the beginning of the operation and a change in the conversion after the operation for 100 hours. The hydrocarbon oils (I) to (m) of the present invention are each suitably used as a hydrocarbon oil for hydrogen production for a hydrogen production system.

In the hydrogen production system of the present invention, a system including at least one device such as a desulfurization reactor, a reformer, and a carbon monoxide purifier is preferable. In particular, (a) a desulfurization reactor, a reformer, Carbon monoxide purifier, (b) desulfurization reactor · reformer · desulfurization reactor (re-desulfurization) · carbon monoxide purifier, (c) reformer · desulfurization reactor · carbon monoxide purifier A deployed system is preferably employed. However, it is not limited to this example. The desulfurization reactor (hereinafter, referred to as desulfurizer) used in the hydrogen production system of the present invention is a device for removing the sulfur content in hydrocarbon oil, and specifically, as a catalyst, a copper-zinc system or a nickele system is used. , Molybdenum, nickel-molybdenum, copanoletomolybdenum, cobalt-nickel-molybdenum, and the like. Particularly, from the viewpoint of desulfurization performance, the catalyst is preferably a copper-zinc catalyst or a nickel catalyst. The reaction conditions must be such that the maximum temperature of the catalyst layer is controlled within the range from the initial boiling point temperature of hydrocarbon oil of 150 ° C to the initial boiling point temperature of hydrocarbon oil + 100 ° C. It is. The maximum temperature of the catalyst layer is preferably at least 30 ° C of the initial boiling point of hydrocarbon oil from the viewpoint of desulfurization performance, and the initial boiling point of hydrocarbon oil + 90 ° from the viewpoint of the durability of the desulfurization catalyst. ° C or lower, more preferably the initial boiling point temperature of the hydrocarbon oil +80 ° C or lower. LHSV is from the point of impact on the size of the desulfurizer, 0. LH ¹ or more preferably, 0. 3 h one ¹ or more, and preferably 1 O h- ¹ or less from the viewpoint of desulfurization performance, 5 h one ¹ or less is more preferred. The reaction pressure (absolute pressure) is preferably less than IMPa, more preferably 0.1 IMPa or less, in terms of installation of a stationary fuel cell in a home or commercial area. In addition, it is preferable that the entrainment of hydrogen into the desulfurizer is not performed in view of the efficiency of the fuel cell system including the hydrogen production system (including the desulfurizer). That's right. The desulfurization operation is preferably carried out so that the sulfur content of the hydrocarbon oil is preferably 0.1 mass ppm or less, more preferably 0.05 mass ppm or less. The reformer is a device for reforming hydrocarbon oil to obtain hydrogen, and specific examples include, but are not limited to, the following.

(1) Steam reforming reformer

The steam reforming reformer mixes heated and vaporized hydrocarbon oil with steam, and uses a Group VIII element of the periodic table as an active metal as a catalyst to obtain a product containing hydrogen as a main component. It is a reformer.

The active metal of the catalyst used in the steam reforming type reformer is preferably ruthenium, rhodium, platinum or the like, particularly preferably ruthenium or rhodium, from the viewpoint of reforming reactivity for obtaining hydrogen from a hydrocarbon compound. The reaction temperature is preferably at least 400 ° C from the viewpoint of reforming reactivity, more preferably at least 500 ° C, and is preferably at most 1,000 ° C from the viewpoint of suppressing the amount of coking generated on the catalyst. The following are more preferred. The mixing ratio (SZC) of water and hydrocarbon oil is preferably 1 mol / mol or more, more preferably 2 mol / mol or more, from the viewpoint of suppressing the amount of coking generated on the catalyst, and 5 mol Z from the viewpoint of reformer efficiency. Mol or less, more preferably 4 mol or less Z mol.

(2) Autothermal reformer

The autothermal reforming type reformer mixes heated and vaporized hydrocarbon oil with steam and air, and uses a Group VIII element of the periodic table as an active metal as a catalyst to obtain a product containing hydrogen as a main component. It is a reformer.

The active metal of the catalyst used in the autothermal reforming reformer is preferably ruthenium, rhodium, platinum or the like, particularly preferably ruthenium or rhodium, in view of the reforming reactivity for obtaining hydrogen from a hydrocarbon compound. . The reaction temperature is preferably at least 400 ° C from the viewpoint of reforming reactivity, more preferably at least 500 ° C, and is preferably at most 1,000 ° C from the viewpoint of suppressing the amount of coking generated on the catalyst. The following are more preferred. The mixing ratio (S / C) of water and hydrocarbon oil is preferably 0.5 mol / mol or more, more preferably 1 mol / mol or more, from the viewpoint of suppressing the amount of coking generated on the catalyst, and from the viewpoint of reformer efficiency. It is preferably 5 mol Z or less, more preferably 3 mol or less. acid The mixing ratio (o ₂ Zc) of hydrogen and hydrocarbon oil is preferably 0.1 mol / mol or more, more preferably 0.2 mol mol or more, from the viewpoint of reforming reactivity. In this respect, the amount is preferably 0.5 mol mol or less, more preferably 0.4 mol / mol or less.

In the "mixing ratio of water and hydrocarbon oil (SZC)" in the present invention, S means the number of moles of water (molecule), and C means the number of moles of carbon in the hydrocarbon oil (molecule). Therefore, the method of obtaining the “mixing ratio of water and hydrocarbon oil (s / c)” will be described with an example. Water (molecule): 6 moles and ethane (C ₂ H ₆ ): When 1 mole is used, the mixing ratio (SZC) of water and hydrocarbon oil is as follows: Since the number of moles of carbon in 1 mole of hydrocarbon oil is 2 moles, “SZC = 6 moles 2 Mol = 3 ". Similarly, in the “mixing ratio of oxygen and hydrocarbon oil (0 ₂₀₎ ” in the present invention, o ₂ is the number of moles of oxygen (molecule), and C is the number of moles of carbon in hydrocarbon oil (molecule). Therefore, the method of obtaining the “mixing ratio of oxygen and hydrocarbon oil (o ₂ / c)” will be described by giving an example. Oxygen (molecule): 0.6 mole and hydrocarbon When ethane (C ₂ H ₆ ): 1 mole is used as the oil, the mixing ratio of oxygen and hydrocarbon oil (0 ₂ / C) is as follows: Ethane, which is hydrocarbon oil: The number of moles of carbon in 1 mole is 2 Therefore, “〇 ₂ 〇 = 0.6 mol / 2 mol = 0.3.” The carbon monoxide purifier is contained in the gas generated in the reformer, and is a catalyst poison for fuel cells. The following are examples of carbon monoxide purifiers.

(1) Water gas shift reactor

The water gas shift reactor mixes the reformed gas obtained from the reformer with steam that has been heated and vaporized, and serves as a catalyst selected from the group IB, IIB, IV, and VIH of the periodic table. Or a reactor that uses two or more elements to obtain carbon dioxide and hydrogen as products from carbon monoxide and water vapor.

The active metal of the catalyst used in the water gas shift reactor is preferably copper, zinc, chromium, iron, platinum, ruthenium, rhodium, or the like, and more preferably copper, zinc, or platinum. The reaction temperature is preferably 100 ° C. or higher in terms of reactivity, more preferably 200 ° C. or higher, and is preferably 60 ° C. from the viewpoint of suppressing coke deposition on the shift catalyst. The temperature is preferably 0 ° C or lower, more preferably 500 ° C or lower. The ratio of water and carbon monoxide in the reformed gas is preferably 1 mol Z mol or more, more preferably 2 mol mol or more, from the viewpoint of stably performing the reaction. Mol / mol or less is preferable, and 10 mol / mol or less is more preferable.

(2) Selective oxidation reactor

The selective oxidation reactor mixes the reformed gas obtained from the reformer with compressed air, uses copper, nickel, platinum, ruthenium, rhodium, etc. as a catalyst, and has a reaction temperature of 100 to 300 ° C. , Gas space velocity 1 00 0 ~ :! OOOO h Reaction pressure Less than IMP a, ratio of air to carbon monoxide in reformed gas 0.5-3.0 mol Z mol, from carbon monoxide and air to carbon dioxide It is a reactor for conversion. Since the hydrocarbon oil (I) of the present invention is excellent in desulfurization performance, it is preferably used as a hydrocarbon oil for hydrogen production for a hydrogen production system provided with a desulfurization reactor. Therefore, in the hydrogen production system using the hydrocarbon oil (I) of the present invention, it is necessary to arrange at least a desulfurization reactor.

Since the hydrocarbon oil (II) of the present invention can reduce the generation of carbon monoxide in the reformed gas, the hydrogen production using the above-described carbon monoxide purifier, particularly the water gas shift reactor, is provided. Hydrogen production efficiency can be increased by being used as a hydrocarbon oil for hydrogen production in systems. Therefore, it is necessary to arrange at least a carbon monoxide purifier in the hydrogen production system using the hydrocarbon oil (II) of the present invention.

Further, the hydrocarbon oil (II) of the present invention is suitably used as a raw material for a hydrogen production system having the steam reformer or the autothermal reformer described above. The reformer is a device for reforming hydrocarbons to obtain hydrogen, and by using the hydrocarbon oil (m) of the present invention, the durability of the reformer can be further improved, and as a result, hydrogen can be obtained. The durability of the manufacturing system is improved. Therefore, it is necessary to arrange at least a reformer in the hydrogen production system using the hydrocarbon oil (II) of the present invention. [Industrial applicability]

The hydrocarbon oil for hydrogen production of the present invention can obtain a stable and high desulfurization rate. The reforming efficiency is high, and the performance of the reformer can be maintained for a long time. In addition, since the amount of carbon monoxide generated in the reformed gas is suppressed and the hydrogen generation efficiency is high, it is suitable as a hydrocarbon oil for hydrogen production.

[Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The general properties of the hydrocarbon oil were measured by the following test methods.

(1) Density refers to the density measured by JIS K 2249 “Density test method for crude oil and petroleum products, as well as density / mass / volume conversion table”.

(2) Flash point refers to the flash point measured by JIS K 2265 “Crude oil and petroleum products-Flash point test method”.

(3) Distillation properties (Ι Β Ρ, Τ10, Τ50, Τ90, Τ95, Ρ Ρ) are all measured by JISK 2254 `` Petroleum product monodistillation test method-normal pressure distillation test method '' Value.

(4) The sulfur content refers to the sulfur content measured by ASTM D4045-96 “Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric ColorimetryJ”.

(5) The aromatic, olefin and saturated components are the aromatic content, olefin content, and saturated hydrocarbon content measured by the fluorescent indicator adsorption method of JIS K2536 “Testing Methods for Hydrocarbons of Petroleum Products”. Refers to the content (including naphthenic hydrocarbons).

(6) The naphthene content refers to the naphthenic hydrocarbon content measured by a method based on ASTM D2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry).

(7) Oxidation onset temperature refers to the temperature measured using a high-pressure differential scanning calorimeter, as described above.

(8) The ratio of the component of the hydrocarbon having 13 carbon atoms refers to a value measured by GC-FID according to the gas chromatography method described above.

(9) CZH conforms to ASTM D 5291-01 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry) Refers to the value measured by the method.

(10) Smoke point refers to the smoke point measured in accordance with JIS K2 537 “Petroleum products – kerosene and aviation turbine fuel oil – smoke point test method”.

"Example;! ~ 2 and Comparative Examples 1 ~ 3 >>

Hydrocarbon substrates (I-1) to (I-13) were manufactured under the conditions shown in Table 1, and the hydrocarbon substrates (1-1) to (I-13) were blended and shown in Table 2. Hydrocarbon oils (I-A) to (I-D) were produced. Table 2 shows the properties.

The obtained hydrocarbon oils (I-A) to (I-D) were evaluated by the desulfurization evaluation device shown in FIG.

Hydrocarbon oil was introduced by a pump into a reaction tube filled with a desulfurization catalyst (nickel-based, (i »2 mm, filled at 50 niL)).

First, the sulfur content of the hydrocarbon oil after desulfurization was measured under the reaction condition <S>, and the desulfurization rate was calculated. After that, the reactor was operated under the reaction condition <A> for 200 hours, returned to the reaction condition S again, the sulfur content of the hydrocarbon oil after desulfurization was measured, and the desulfurization rate was calculated. Then, the change in the desulfurization rate before and after the operation for 200 hours was compared.

Reaction conditions S>

The catalyst layer maximum temperature: initial boiling point temperature one 1 0 ° C of a hydrocarbon oil, LHS V: lh one ^1, reaction pressure (absolute pressure): 0. 05MP a

Reaction conditions <A>

Maximum temperature of catalyst layer: Initial boiling point of hydrocarbon oil + 10 ° C, LHS V: 5 h- \ Reaction pressure (absolute pressure): 0.05 MPa Also, Comparative example of reaction conditions (Comparative example 3) The desulfurization reaction was performed under the following reaction conditions <A,> and <S '>, and the changes in the desulfurization rate were compared.

Reaction conditions s,>

Catalyst bed maximum temperature: Initial boiling point temperature of hydrocarbon oil + 11 o ° c,

LHS V: 0.5 h ~ Reaction pressure (absolute pressure): 0.05 MPa

Reaction conditions <A '>

Maximum temperature of catalyst layer: Initial boiling point of hydrocarbon oil + 1 30 ° C, LHS V: 5 h "\ Reaction pressure (absolute pressure): 0.05 MPa The hydrocarbon oils (I-A) to (I-D) were evaluated as described above, and the evaluation results are shown in Table 3.

From the results shown in Table 3, when the hydrocarbon oils (I-A) and (I-B) of the present invention were used, the initial operation was 200 hours after the operation compared with the comparative example. It can be seen that the desulfurization rate was high and the rate of decrease in the desulfurization rate after 200 hours of operation was small. The rate of decrease in the desulfurization rate was calculated by (desulfurization rate at the beginning of operation—desulfurization rate after 200 hours) × 100 desulfurization rate at the beginning of operation (%).

<< Examples 3 to 5 and Comparative Examples 4 to 6 >>

Hydrocarbon substrates (Π_1) to (Π-5) were manufactured under the conditions shown in Table 4. Hydrocarbon oils (Π_Α) to (Π-Ε) are produced by blending hydrocarbon base materials (Π-1) to (Π-5), and their properties are shown in Table 5.

The obtained hydrocarbon oils (Π-Α) to (Π-Ε) are shown in the evaluation flowcharts shown in FIGS. 4 and 5 (evaluation apparatuses 1 and 2 including a reformer and a carbon monoxide purifier). ) Was evaluated as follows.

The difference between the two evaluation devices is the type of reformer. The evaluation conditions are as follows.

The hydrocarbon oil preheater, steam generator and air preheater are each set at 300 ° C.

(Reformer)

The reaction temperature of the steam reformer is 650 ° C, LHS V: 1 h ~ The mixing ratio of water and hydrocarbon oil (S / C): 3.0 molmol, and the reaction temperature of the autothermal reformer is 650 ° C, LHSV: 1 h ~ H 2 0 / C 2. 0 mol mol, oxygen and the mixing ratios of hydrocarbon oil (〇 ₂ / C): was operated at 0.3 mole Z moles conditions.

(Carbon monoxide purifier)

In Examples 3 to 5 and Comparative Examples 4 to 5, the reaction temperature was 250 ° C. Comparative Example 6 was operated under the conditions of a carbon monoxide ratio: 5 mol Z mol and a reaction temperature: 90 ° C., and a carbon monoxide ratio in water and reforming gas: 5 mol mol.

(1) Evaluation device 1: Steam reformer + water gas shift reactor

Hydrocarbon oil and water, which have been desulfurized in advance by a desulfurizer, are vaporized by electric heating, respectively, filled with a noble metal catalyst, and led to a reactor (reformer) maintained at a predetermined temperature by an electric heater. A reformed gas rich in hydrogen was generated. The water contained in the reformed gas was separated from the reformed gas by a gas-liquid separator using a cooling method.

Next, a reactor (water gas shift reactor) in which the reformed gas and a mixed gas to which a certain amount of steam was added to the co concentration in the reformed gas was maintained at a predetermined temperature by an electric heater filled with a copper-zinc catalyst. ) And converted carbon monoxide in the reformed gas to carbon dioxide.

(2) Evaluation device 2: Autothermal reformer + water gas shift reactor

Hydrocarbon oil and water, which have been desulfurized in advance by a desulfurizer, are vaporized by electric heating, respectively, and the mixture of heated air is filled with a noble metal catalyst and maintained at a predetermined temperature by an electric heater. To a reactor (reformer) that generated hydrogen-rich reformed gas. Water contained in the reformed gas was separated from the reformed gas by a gas-liquid separation tube using a cooling method.

Next, a reactor (water gas shift reactor) in which the reformed gas and a mixed gas to which a certain amount of steam was added to the co concentration in the reformed gas was maintained at a predetermined temperature by an electric heater filled with a copper-zinc catalyst. ) And converted carbon monoxide in the reformed gas to carbon dioxide. A gas chromatograph capable of analyzing the gas composition and unreacted hydrocarbon oil was installed at the outlet line of the reformer and the outlet line of the water gas shift reactor of the evaluation devices 1 and 2.

Based on the results of the composition analysis by gas chromatography, the hydrogen / CO ratio (H ₂ / CO) was calculated at the outlet of the reformer and the outlet of the water gas shift reactor, and the hydrocarbon / oil / water gas shift reactor The comparison was made for the case where the reaction conditions were changed. These evaluations were made for each of the hydrocarbon oils (Π-Α) to (Π-Ε), and the evaluation results are shown in Table 6.

From the results shown in Table 6, when the hydrocarbon oils (Π-Α) to (Π-C) of the present invention were used, the amount of hydrogen generated with respect to carbon monoxide was smaller than that of the comparative example. You can see that it is expensive.

<< Examples 6 to 7 and Comparative Examples 7 to: 10 >>

Hydrocarbon substrates (ΊΠ-1) to (基材 _5) were manufactured under the conditions shown in Table 7. Hydrocarbon base materials (III-1) to (III-15) are blended to produce hydrocarbon oils (III-A) to (III [-E), and their properties are shown in Table 8.

The obtained hydrocarbon oils (Π_Α) to (ΙΠ-Ε) were evaluated as follows in accordance with the evaluation flow charts shown in FIGS. 6 and 7.

The hydrocarbon oil preheater, steam generator and air preheater are set at 300 ° C respectively.

(1) Steam reforming evaluation

Fig. 6 shows a flowchart of the steam reforming evaluation. Hydrocarbon oil and water are vaporized by electric heating, respectively, filled with a reforming catalyst (ruthenium-based, φ2πιιη, filling volume 5 mL), and led to a reforming reaction tube maintained at a predetermined temperature by an electric heater, and hydrogen content is reduced. A rich reformed gas was generated.

First, a reforming reaction was performed under the following reaction conditions S1.

(Reaction condition S 1)

LHSV: 0.5 h-\ S / C: 3 mol Z mol, catalyst layer outlet temperature: 650 ° C After determining the conversion under reaction condition S1, the oil was passed for 100 hours under the following reaction condition A1 Was done.

(Reaction condition A 1)

LHS V: 5 h " ¹ , S / C: 3 mol Z mol, catalyst layer outlet temperature: 650 ° C After operating under reaction condition A1, return the reaction condition to S1, measure the conversion, and measure the initial operation. Was calculated.

These evaluations were performed for each of the hydrocarbon oils (m−A) to (m−E). The results are shown in Table 9. Further, as a comparative example of the reaction conditions, the reforming reaction was performed under the following reaction conditions S1.

(Reaction conditions S 1 ')

LHS V: 0.5 h ~ S / C: 0.8 molmol, catalyst layer outlet temperature: 6

50 ° C

After the conversion was determined under the reaction conditions S I ′, the oil was passed for 100 hours under the following reaction conditions A 1 ′.

(Reaction condition A1 ')

LHS V: 5 h ~ S / C: 0.8 mol / mol, catalyst layer outlet temperature: 650. C After the operation under the reaction condition A 1 ′, the reaction condition was returned to S 1 ′, the conversion was measured, and the change in the conversion from the initial operation was calculated. The results are shown in Table 9 as Comparative Example 10.

(2) Evaluation of autothermal reforming

FIG. 7 is a flowchart of the autothermal reforming evaluation. The hydrocarbon oil and water are vaporized by electric heating, and a reforming catalyst (rhodium, φ2πιπι, filling volume 5 mL) is filled together with the preheated air into a reforming reaction tube maintained at a predetermined temperature by an electric heater. Led to the generation of reformed gas rich in hydrogen.

First, a reforming reaction was performed under the following reaction conditions S2.

(Reaction condition S 2)

LHS V: 0. 5 h ~ \ S / C: 2 mol / _{mol, 0 2 / C: 0. 25} , the catalyst layer outlet temperature: 650 ° C

After determining the conversion under the reaction condition S2, the oil was passed for 100 'hours under the following reaction condition A2.

(Reaction condition A 2)

LHS V: 5 h "\ S / C: 2 mol / _{mol, 0 2 / C: 0. 25} , the catalyst layer outlet temperature: 650 ° C

After the operation under the reaction condition A2, the reaction condition was returned to S2, the conversion was measured, and the change in the conversion from the initial operation was calculated.

These evaluations were made for each of the hydrocarbon oils (ΙΠ-A) to (ΙΠ-E). Table 9 shows the results. As a comparative example of the reaction conditions, a reforming reaction was performed under the following reaction conditions S2. (Reaction conditions S 2 ')

^{LH SV: 0. 5 h "1} , S / C: 0. 3 mol / mol, 〇 ₂ / C: 0. 25, the catalyst layer outlet temperature: 650 ° C

After determining the conversion under the reaction condition S2 ', the oil was passed for 100 hours under the following reaction condition A2'.

(Reaction condition A 2 ')

LHS V: 5 h ~ \ S / C: 0. 3 mo 1 / mo 1, 0 2 / C: 0. 25, the catalyst layer outlet temperature: 650 ° C

After the operation under the reaction condition A2 ', the reaction condition was returned to S2, and the conversion was measured to calculate the change in the conversion from the initial operation. The results are shown in Table 9 as Comparative Example 10. The conversion was measured as follows. Each reforming evaluation device is equipped with a gas flow meter that can measure the flow rate of reformed gas generated at the reaction tube outlet line, and a gas chromatography that can analyze the composition of generated reformed gas and analyze unreacted hydrocarbons. did. The tank for supplying hydrocarbon oil and water was installed on a balance, and the amount of supply to the reaction tube per hour was measured with the balance. The conversion rate of hydrocarbon oil was calculated from the analysis results of hydrocarbon oil supply amount, generated reformed gas flow rate and generated gas composition. The conversion rate is defined as follows.

Conversion (%) CI of == generated gas (C0 _2, CO and CH ₄₎ Ryono supplied from the results shown in C amounts X 1 00 Table 9 in hydrocarbon oils, hydrocarbon oils of the present invention (Iotapai — It can be seen that, when A) and (III-B) are used, the conversion rate is higher and the conversion rate can be stably maintained for a long period of time as compared with the hydrocarbon oil of the comparative example and the equipment conditions. . Hydrocarbon base material I-1 I-1 2 * Properties of feedstock

IBP ° C 155.5-Distillation properties

T90 ° C 234.0-Aromatic content vol% 11.6 1-1 Straight chain saturated hydrocarbon content vol% 40.0-11 Straight chain saturated hydrocarbon content with 10 to 15 carbon atoms vol% 31.4-Sulfur mass ppm 120- (I) Manufacturing conditions

Reaction temperature. C 279-302-Hydrogen pressure Pa 8.5--Process (1): Hydrogenation

LHSV h- ¹ 1.54 - - desulfurization treatment step

Hydrogen / hydrocarbon capacity ratio 0.26 1-Catalyst Ni-W--Process (2): Light fraction

Stripping process Strip volume of light fraction vol% 30--Reaction temperature ° C 190--Process (3): Linear saturation pressure MPa 2--Hydrocarbon extraction Molecular sieve

Removal process Catalyst ― ―

5A

Extraction and removal of saturated hydrocarbons E vol% 28-Properties of base material

Density @ 15 ° C g / cm ³ 0.812 0.799 0.794 Distillation properties IBP ° C 188.0 164.0 153.0

CO

T50 ° C 212.5 203.5 197.0

T90 ° C 235.0 220.0 237.0

EP ° C 251.0 241.0 266.0 Sulfur mass ppm 0.16 0.15 0.25 Aromatic vol% 7.3 14.8 18.2

* A highly hydrodesulfurized kerosene fraction obtained by subjecting Middle Eastern crude to atmospheric distillation. Table 2

Hydrocarbon oil I-A I-B I- G I-D Base compounding ratio Base material (I-1) vol% 100 90

Base material (I-2) vol% 100 Base material (I-3) vol% 10 100 Density @ 15 ° C g / cm 0.8124 0.8102 0.7990 07940 Flash point. c. C 64 66 51.5 70 Distillation properties IBP ° C 188.0 190.0 164.0 197.0

T10 ° C 197.5 201.0 179.0 205.0

T50 ° C 212.5 214.5 203.5 218.0

T90. C 235.0 236.0 220.0 237.0

T95 ° C 241.0 243.5 230.5 251.0

EP ° C 251.0 264.0 241.0 266.0 Sulfur content mass ppm 0.16 0.17 0.15 0.25 Aromatic content vol% 7.3 8.4 14.8 18.2 Orefin content vol% 0.0 0.0 0.4 0.1 Saturation-divided phenol is included) voi% 92.7 91.6 84.8 81.7 Naphthene content vol% 48.0 47.1 43.2 39.4 Oxidation start temperature ° C 218 216 209 215 Proportion of hydrocarbon component with 13 carbon atoms mass% 26.1 21.2 22.3 17.3

Table 3 Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3 Hydrocarbon oil I-AI-BI-CI-DI-D Desulfurization reaction conditions AAAAA 'Maximum catalyst layer temperature ° C Initial boiling point-10 Initial boiling point -10 Initial boiling point-10 Initial boiling point-10 Initial boiling point + 110 Desulfurization rate,%

Initial operation 94 91 47 40 28

After 200 hours operation 91 89 35 29 18 Decrease rate% 3 3 24 28 36 Table 4

* The hydrocarbon oil obtained in steps (1) to (3) was distilled and separated by a series of devices, and the following properties were distilled and separated. * * Kerosene fraction obtained by applying Middle Eastern crude oil to atmospheric distillation device The heavy fraction of the highly hydrodesulfurized ** *** The kerosene fraction obtained by subjecting Middle Eastern crude oil to atmospheric distillation is highly hydrodesulfurized.

Table 5 Hydrocarbon oil Π -Β n -c Π -D Π -Ε Base material (Π— 1) vol% 100

Base material ((—2) vol% 100 95

Substrate blend ratio Substrate (E-3) vol% 5

Base material ((—4) vol% 100

Base material ((-5) vol% 100 Density @ 15 ° C g / cm ³ 0.768 0.791 0.793 0.7503 0.7936 Flash point. c ° C 41 74 76 65 45 Distillation properties IBP ° C 163.0 202.5 205.5 192.5 153.0

T10 ° c 167.5 207.0 215.0 21 1.0 166.5

T50 ° c 170.0 209.0 219.0 233.0 197.0

T90 ° c 174.0 213.0 228.0 237.0 242.0

T95 ° c 175.0 214.0 239.0 247.5 251.5

EP. c 193.5 226.5 250.0 261.0 269.0

T95-IBP ° c 12.0 1 1.5 33.5 55.0 98.5 Saturation (including naphthene) vol% 99.8 99.8 99.6 99.7 81.9 Aromatic vol% 0.2 0.2 0.4 0.3 18.0 Orefin vol% 0.0 0.0 0.0 0.0 0.1 Naphthene vol% 46 56 54 0 24 Sulfur mass ppm 0.08> 0.08 0.16 0.28 0.45 Oxidation start temperature ° C 215 215 214 221 208

C / H mol / mol 2.07 2.02 2.01 2.13 1.92

Table 6

※ decrease comparison, in each of the evaluation, the relative value when 100.0 outlet H ₂ / GO of Comparative Example 4

Table 7

* Highly hydrodesulfurized kerosene fraction obtained by subjecting Middle Eastern crude to atmospheric distillation. ** A kerosene fraction obtained by subjecting a Middle Eastern crude to a normal-pressure distillation unit and highly hydrodesulfurized. ※※※ Normal product kerosene obtained by subjecting Middle Eastern crude oil to atmospheric distillation and hydrodesulfurizing the kerosene fraction.

Table 8 Hydrocarbon oil Π -Α Π -Β m -cm— D mE Base material (m-1) vol% 100--vol%-95---Base material blending ratio Base material (m-3) vol% -5 100--Base material (Π— 4) vol% ―---100

Base material (Π-5) vol%---100 Density @ 15 ° C g / cm ³ 0.794 0.805 0.800 0.796 0.794 Flash point ° c ° C 42.0 50.0 51.5 53.0 45.0 Distillation properties IBP ° c 50.0 161.0 164.0 166.0 153.0 T10. c 166.5 180.5 182.0 170.0 171.0

T50 ° c 191.5 205.5 203.5 210.5 197.0

T90 M C ° c 225.5 233.0 228.5 252.0 239.5

T95 ° c 234.0 246.0 230.0 267.0 249.0

EP ° c 246.0 253.5 246.0 287.0 265.0 Sulfur mass ppm 0.18 0.12 0.15 0.12 4.30 Aromatic vol% 7.9 6.5 14.8 9.5 18.2 Orefin vol% 0.2 0.1 0.2 0.2 0.6 Saturation (including naphthene) vol% 91.9 93.4 85.0 90.3 81.2 Naphthene vol% 47.7 41.8 1--Oxidation start temperature ° C 213 216 209 217 215 Smoke point mm 29 27 25 28 25

Example 6 Example 7 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Hydrocarbon oil Π -Α m -B HI -C Π— D m— Ε m -E

1.Evaluation by steam reforming

Reaction conditions S1 S1 S1 S1 S1 sr Reaction temperature ° c 650 650 650 650 650 650 650

SZG mol Z mol 3.0 3.0 3.0 3.0 3.0 0.8 Conversion

Initial operation 110.5 109.7 100.0 102.5 97.8 88.5

After 100 hours operation 109.7 108.8 92.5 96.1 84.3 69.2 Reduction% 0.8 0.9 7.5 6.4 13.5 21.8

2.Evaluation by autothermal reforming

Reaction conditions S2 S2 S2 S2 S2 S2 'Reaction temperature ° c 650 650 650 650 650 650 650

SZC mol mol 2.0 2.0 2.0 2.0 2.0 0.3

0 ₂ ZG mol Z mol 0.25 0.25 0.25 0.25 0.25 0.25 Conversion

Initial operation 107.3 107.0 100.0 102.0 97.0 83.1

After 100 hours operation 106.4 106.1 91.8 95.5 82.7 61.3 Reduction rate% 0.9 0.9 8.2 6.5 14.3 26.2

* The conversion rate is a relative value when the conversion rate in the initial operation of Comparative Example 7 was set to 100.0 in each reforming evaluation.

[Brief description of drawings]

FIG. 1 is a graph showing an example of a correlation curve between the calorific value of hydrocarbon oil and temperature measured using a high pressure differential scanning calorimeter.

FIG. 2 is a graph showing a differential curve of the correlation curve shown in FIG.

Figure 3 is a flowchart of the evaluation system including the desulfurizer.

Figure 4 is a flowchart of the evaluation system including the steam reforming reformer and the water gas shift reactor.

Fig. 5 is a flow chart of the evaluation system including the autothermal reforming reformer and the water gas shift reactor.

FIG. 6 is an evaluation flowchart of the steam reforming type reformer.

Figure 7 is an evaluation flow chart of the autothermal reformer.

Claims

The scope of the claims

1-Initial boiling point is 140-180 ° C, 90% by volume Distilling temperature is 200-270 ° (: Aromatic content is less than 20% by volume, linear saturated hydrocarbon content is more than 25% by mass, charcoal Using a hydrocarbon mixture having a linear saturated hydrocarbon content of a prime number of 10 to 15 of 20% by mass or more and a sulfur content of 300% by mass or less as a feed oil, the mixture is obtained through the following steps (1) to (3). The first boiling point is 160 ° C or more and 200 ° C or less, the 50% by volume distillation temperature is 200 ° C or more and 220 ° C or less, and the 90% by volume distillation temperature is 220 ° C. ° C to 245 ° C, aromatic content 10% by volume or less, sulfur content 0.5 mass ppm or less, naphthene content 40% by volume or more, oxidation start temperature 210 ° C or more, 13 carbon atoms Hydrocarbon oil for hydrogen production in a hydrogen production system provided with at least a desulfurization reactor, characterized in that the proportion of hydrocarbons is 20% by mass or more.

Step (1):. Feedstock oil, a reaction temperature two hundred and fifty to three hundred ten ° C, the hydrogen pressure 5~1 OMP a, LHS V 0. 5~3 0 h 1, hydrogen Z hydrocarbon volume ratio 0.1 5-0. Under the conditions of 6, depending on the catalyst containing Ni-W, Ni-Mo, Co-Mo, Co-W, or Ni-Co-Mo, Hydrodesulfurization process

Step (3): After stripping the light components, extracting and removing 10% by volume or more of linear saturated hydrocarbons by zeolite at a temperature of 150 to 250 ° C and a pressure of 1 to 5 MPa.

2. Initial boiling point: 140-180 ° C, 90% by volume Distilling temperature: 200-270 ° C, Aromatic content: 20% by volume or less, Straight chain saturated hydrocarbon content: 25% by mass or more, Number of carbon atoms A hydrocarbon mixture having a linear saturated hydrocarbon content of 10 to 15 of 20% by mass or more and a sulfur content of 300% by mass or less is used as a feedstock and obtained through the following steps (1) to (4). It contains hydrocarbon base material, 95% by volume distillation temperature is 240 ° C or less, difference between 95% by volume distillation temperature and initial boiling point is 50 ° C or less, and sulfur content is 0.5 mass p pm or less, the molar ratio of carbon to hydrogen is 1.95 or more, the naphthene content is 40% by volume or more, the aromatic content is 10% by volume or less, and the oxidation start temperature is 210 ° C or more. Hydrocarbon oil for hydrogen production in a hydrogen production system equipped with at least a carbon monoxide purifier.

Step (1):.. Feedstock oil, a reaction temperature two hundred and fifty to three hundred and ten ° C, the hydrogen pressure 5~1 OMP a, LHS V 0. 5~3 0 h 1, hydrogen / hydrocarbon volume ratio from 0.15 to 0 6 Hydrodesulfurization treatment with a catalyst containing one selected from the group consisting of Ni—W, Ni—Mo, Co—Mo, Co—W, and Ni—Co—Mo Process

Step (3): After stripping light components, extracting and removing 10% by volume or more of linear saturated hydrocarbons by zeolite under the conditions of a temperature of 150 to 250 ° C and a pressure of 1 to 5 MPa.

Step (4): Step of fractionating the hydrocarbon oil from which the straight-chain saturated hydrocarbons have been extracted and removed in Step (3)

3. Initial boiling point: 140 ~: 180 ° C, 90% by volume Distilling temperature: 200-270 ° C, Aromatic content: 20% by volume or less, Linear saturated hydrocarbon content: 25% by mass or more, Charcoal A hydrocarbon mixture having a linear saturated hydrocarbon content of a prime number of 10 to 15 of 20% by mass or more and a sulfur content of 300% by mass or less is used as a feedstock, and the following steps (1) to (3) and ( It contains a hydrocarbon base material obtained through 5), has a flash point of 40 ° C or higher and an initial boiling point of 145. C to 170 ° C or less, 50% by volume distillation temperature 180 ° C to 220 ° C or less, 95% by volume distillation temperature 220 ° C to 260 ° C or less, sulfur content 0.5 mass Hydrogen production in a hydrogen production system equipped with at least a reformer, characterized in that the peak temperature is less than 26 pm, the smoke point is 26 mm or more, the aromatic content is 10% by volume or less, and the oxidation start temperature is 210 ° C or more. For hydrocarbon oils.

Step (1): Feed oil at a reaction temperature of 250 to 310 ° C, hydrogen pressure of 5 to ¹ OMPa, LHSV of 0.5 to 3.0 h1, hydrogen / hydrocarbon capacity ratio of 0.15 to 0.6 Subject to hydrodesulfurization treatment with a catalyst containing one selected from the group consisting of Ni—W, Ni—Mo, Co—Mo, Co—W, and Ni—Co—Mo. Process

Step (2): Stripping 1 to 35% by volume of light components from the hydrodesulfurized oil obtained in Step (1) Step (3): After stripping light components, extract and remove 10% by volume or more of linear saturated hydrocarbons with zeolite under the conditions of a temperature of 150 to 250 ° C and a pressure of 1 to 5 MPa.

Step (5): The hydrocarbon obtained in Step (3) or the hydrocarbon obtained in Step (4) is fractionated with the hydrocarbon obtained in Step (3). Mixing 60% by volume or more of the light components stripped in

4. Under the reaction pressure (absolute pressure) of the desulfurization reactor of less than 1 MPa, the maximum temperature of the desulfurization catalyst layer is changed from the initial boiling point temperature of the hydrocarbon oil-50 ° C to the hydrocarbon oil described in Paragraph 1. A hydrogen production system equipped with a desulfurization reactor for controlling the temperature within the range of the initial boiling point of hydrogen oil + 10 o ° C for desulfurization

5. A mixture of the reformed gas obtained by reforming the hydrocarbon oil described in Paragraph 2 and steam, and one of the members selected from Groups IB, IIB, VI, and VIII of the Periodic Table Alternatively, in the presence of a catalyst containing two or more elements as active metals, the reaction temperature is 100 to 600 ° C, and the molar ratio of water to carbon monoxide in the reformed gas is 1 to 80 mol / mol. A hydrogen production system comprising a water gas shift reactor for obtaining carbon dioxide and hydrogen as products from carbon and steam.

6. A mixed gas of the hydrocarbon oil and steam described in Paragraph 3 in the presence of a reforming catalyst containing a Group VIII element of the periodic table as an active metal at a reaction temperature of 400 to 100 ° C and water. A hydrogen production system equipped with a steam reforming reformer that obtains a product containing hydrogen as a main component by reacting with a hydrocarbon oil at a mixing ratio of 1 to 5 mol mol.

7. hydrocarbon oil according to paragraph 3, a mixed gas of steam and air, the presence of a reforming catalyst comprising a Group VIII element as the active metal, the reaction temperature 400 to 10 00 ^D C, and water By reacting with a mixture ratio of hydrocarbon oil of 0.5 to 5 mol mol and a mixture ratio of oxygen and hydrocarbon oil of 0.1 to 0.5 mol / mol, a product mainly composed of hydrogen is obtained. A hydrogen production system equipped with a self-thermal reforming reformer.

8. The hydrogen production system according to any one of items 4 to 7, comprising a desulfurization reactor, a reformer, and a carbon monoxide purifier.